US2907738A - Mixed resin acid esters of 4, 4-bis(4-hydroxyaryl) pentanoic acid - Google Patents
Mixed resin acid esters of 4, 4-bis(4-hydroxyaryl) pentanoic acid Download PDFInfo
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- US2907738A US2907738A US519279A US51927955A US2907738A US 2907738 A US2907738 A US 2907738A US 519279 A US519279 A US 519279A US 51927955 A US51927955 A US 51927955A US 2907738 A US2907738 A US 2907738A
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- United States
- Prior art keywords
- acid
- hydroxyaryl
- bis
- parts
- acids
- Prior art date
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims description 26
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 title claims description 18
- 239000000203 mixture Substances 0.000 claims description 33
- 239000000025 natural resin Substances 0.000 claims description 22
- 150000005846 sugar alcohols Polymers 0.000 claims description 20
- -1 HYDROXYPHENYL Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 40
- 239000000047 product Substances 0.000 description 23
- 150000007513 acids Chemical class 0.000 description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 17
- 238000005886 esterification reaction Methods 0.000 description 16
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000032050 esterification Effects 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000002924 oxiranes Chemical class 0.000 description 5
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 4
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 4
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 4
- 125000001931 aliphatic group Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 150000004715 keto acids Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000012262 resinous product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 2
- 241000592335 Agathis australis Species 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004859 Copal Substances 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 241000782205 Guibourtia conjugata Species 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 240000008548 Shorea javanica Species 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N alpha-methylfuran Natural products CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229940040102 levulinic acid Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- SQHKJSPPFSVNDF-UHFFFAOYSA-N 1,2,2,3-tetrakis(hydroxymethyl)cyclohexan-1-ol Chemical compound OCC1CCCC(O)(CO)C1(CO)CO SQHKJSPPFSVNDF-UHFFFAOYSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- XIKCAYKPVQCBJM-UHFFFAOYSA-N 2,2-bis(4-hydroxyphenyl)pentanoic acid Chemical compound C=1C=C(O)C=CC=1C(C(O)=O)(CCC)C1=CC=C(O)C=C1 XIKCAYKPVQCBJM-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- HOVAGTYPODGVJG-ZFYZTMLRSA-N methyl alpha-D-glucopyranoside Chemical compound CO[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O HOVAGTYPODGVJG-ZFYZTMLRSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
Definitions
- This invention relates to new compositions which are mixed esters ofpolyhydric alcohols, natural resin,acids,
- reaction products having unusually good chemical resistance, hardness, gloss, etc.
- compositions of this invention being esters of polyhydric alcohols and mixtures of natural resin acids and hydroxyaryl-substituted aliphatic acids, are relatively high molecular weight resinous polyhydric phenols.
- the number of phenolic groups per molecule. are dependent on the number of alcoholic hydroxyl groups present in the polyhydric alcohol esterified, as well as on the amounts and proportions of natural resin acid and hydroxyaryl-substituted aliphatic acid used in the preparation of the esterified product.
- the mixed esters of this invention combine within the same chemical molecule natural resin acid esters and a phenolic residue, the natural resin acid ester portion being similar to the natural resin acid portion presentin the so-called ester gums which are natural resin acid esters of polyhydric alcohols.
- This property renders the compositions of this invention particularly valuable in the manufacture of complex products such as coating and molding compositions, where the natural resin acid esters are desirable for the purpose of contributing hardness and gloss to the finished product.
- the phenolic residues present in the compositions and introduced by the hydroxyaryl-substituted aliphatic acids contribute reactive phenolic hydroxyl groups which for the most part do not enter into the esterification reaction used in the preparation of the mixed esters of this invention.
- Esterification of the phenolic hydroxyl groups of the phenolic residue with dibasic acids would also give polymerization in which the natural resin acid ester becomes an intimate part of the final polymer chemical composition.
- Such esterification reactions involving the phenolic hydroxyl groups would conveniently be carried out by heating with a mixture of the dibasic acid and acetic anhydride.
- hydroxyarylsubstituted aliphatic acids contemplated for use in preparing the desired resinous polyhydric phenols have two hydroxyphenyl groups attached to a single carbon atom.
- the preparation of these substituted acids may be most conveniently carried out by condensing a keto-acid with the desired phenol.
- a terminal carbon atom as used herein refers to primary carbon atoms other than the carboxyl carbon atom of the keto-acid.
- Diphenolic Acid a trademark of S. C. Johnson & Son, Inc.
- DPA a trademark of S. C. Johnson & Son, Inc.
- the phenolic nuclei of the Diphenolic Acid may be substituted with any groups which will not interfere with the esterification reactions.
- the nuclei may be alkylated as disclosed in Serial No. 489,300 or they may be halogenated.
- the Diphenolic Acid derived from 1 mol of levulinic acid and 2 mols of phenol is particularly advantageous in that it may be readily prepared to a high degree of purity, whereas the use of substituted phenols, such as the alkylated products, usually results in. mixed compositions which are less readily purified.
- substituted phenols such as the alkylated products
- the Diphenolic Acid derived from alkylated phenols are more desirable than those derived from the nonalkylated product on the basis that the alkyl groups tend to give better organic solvent solubility, flexibility, and better water resistance.
- the natural resin acids which may be used with these hydroxyaryl-substituted acids in the co-esterification of the polyhydric alcohols are illustrated by the commercial grades of rosin and other natural-occurring acid resins, such as the kauri, copal, damar, and Congo gums.
- Typical commercial grades of rosin for example, have acid values of, around 150-175. Acid values as used herein are defined as the number of milligrams of KOH required to neutralized the acid present in a one-gram sample.
- Typical damar gums have acid values ranging from 18 to 60.
- Kauri gums have acid values of from 60-80, while copal gums have acid values in the range of -130.
- the essential composition or" all these natural-occurring resin acids are cyclic terpenic type acids of which abietic acid is fairly typical.
- the polyhydric alcohols may be the nonresinous type or the resinous type. These polyhydric alcohols, because of their polyfunctionality, will esterify with natural resin acids and hydroxyaryl-substituted acids to give a resinous phenolic product.
- nonresinous type polyhydric alcohols are such materials as ethylene glycol, polyethylene glycols, propylene glycol, polypropylene glycols, 1,3-butane diol, 2,5-pentane diol, 1,6-hexane diol, neopentyl glycol, glycerol, erythritol, pentaerythritol, polypentaerythritols, sorbitol, mannitol, alpha methyl glucoside, polyallyl alcohols, diethanolamine, triethanolamine, and tetramethylol cyclohexanol
- the resinous p y y alcohols Which y be used Esterifieation of either the nonresinous or resinous in the preparation of the subject esters may be illustrated polyhydric l h l with Di henoli A id and natural y Such materials as the l'esinells Iea
- the Water ployed may be illustrated by those which are prepared b r d by rmitti itto olatilize during esby the'reaction of phenol-formaldehydecondensates with teriiication, Rgmoval f thelwam-vmayp also-be fadchlorohydrins.
- analkylphenol m y b Contated by continuously bubblin gthrough the reaction mixdells'ed With formaldehyde, followed y treatment of 8m ture during esterification a stream of inert gas, such as alkaline solution of this intermediate methylol derivative carbon di id nitrogen, It is al o sometimes conven- With chlerohydrln, Such as glycerol'mollqehlorohydfini lent to. facilitate the water removal bycarrying out the to y d after condensation a Polymeric p y y aleoreaction in a vessel provided. with condenser attached 'hol.
- This resinous polyhydric alcohol may then be'used thereto through a water trap, adding a suflicient amount in esterification with the diphenolic acids to prepare the of a volatile, water-insoluble. solvent to give reflux at the subject resinous polyhydric phenols; esterification temperature, continually removing the wa- A yp formula for a p i n r n descri ter by azeotropic distillation and permitting the solvent may be illustrated by the following reaction between equal to return to the reaction mixture after having dropped the molar portions of ethylene glycol, abietic acid, and 4,4- water in the water trap. V bis(4-hydroxyphenyl)pentanoic acid.
- Abietic acid is the The order of addition of the various ingredients, Di- "chief acid ingredient of commercial rosin and is typical phenolic Acid, resin acids, and polyhydric alcohols, to of the terpenic type acids present in the natural resin each other may be varied. It is sometimes advantageous acids. to vary this order of addition to obtain optimum results H3O GOZH HOG onioniooin H 0 0 V on OH OH heat C +l 1 ll a A g on on,
- Examples I to VI illustrate the preparation of some as esterification of the alcoholic 'hydroxyl groups by the polyhydric alcohol esters of inixturesof Diphenolic'Acid natural resin acids. For the most part, however, the more 7 and-natural resin acid esters. These reactions are in all reactive alcoholic hydroxyl groups of the polyhydric al cases carried out in vessels provided with a thermometer, 'cohols tend-to-esterify to a greater extent than the phenola mechanical agitator, and a condenser attached through ydroxyl groups. These compositions are valuable in a water trap. Inert gas was bubbled through the reacform'ulating useful products in the coat ngs, molding, tion mixtures throughout esterification so as to remove and adhesive field. l water formed in the esterification.
- Example 11 A mixture of 143 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid, 165 parts of commercial rosin, and 34 parts of ethylene glycol was esterified to an acid value of 7 yielding a product having a softening point of 81 C.
- Example III In a reaction vessel provided with a mechanical agitator was placed 452 parts of bis(4-hydroxyphenyl)isopropylidene dissolved in 1500 parts of water containing 82 parts of sodium hydroxide. The temperature of the continuously agitated solution was raised to 60 C. and 93 parts of epichlorohydrin was added slowly at 60-65 C. After addition of the epichlorohydrin was complete, the temperature was gradually raised to 95 C. and held at this temperature for a period of 1 hour. A solution of 82 parts of sodium hydroxide dissolved in 500 cc. of
- Example IV A mixture of 143 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid, 165 parts of commercial rosin, and 37 parts of pentaerythritol was esterified to an acid value of 7.5 to yield a product having a melting point of 126 C.
- Example V A mixture of 174 parts of Epon 1004 and 101 parts of commercial rosin was esterified to an acid value of 19 at which point 86 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid was added and esterification continued until an acid value of 139 was reached, giving a product having a softening point of 131 C.
- Example VII A mixture of parts of the resinous product of Example I, 21 parts of 38% aqueous formaldehyde, .063 part of oxalic acid and 17 parts of xylol was heated with continuous agitation for a period of 1 hour and 30 minutes at 95 C., after which the water layer was removed by decantation. The organic resin layer was heated with agitation to C. at a reduced pressure of around 30-40 mm. in order to remove the last traces of water.
- This varnish was treated with 03% cobalt naphthenate drier and 3% lead naphthenate drier based on Example VIII
- the mixed esters of this invention may be modified to some extent by incorporating with the esters other constituents.
- These constituents maybe inert constituents such as fillers, pigments, or certain plasticizers, or they may contain functional groups and enter into the esterification of the polyhydric alcohols with natural resin acids and hydroxyaryl-substituted acids so as to be chemically carried by the mixed esters of this invention.
- a new composition of matter comprising the mixed ester of a fusible polyhydric alcohol, a natural resin acid, and a pentanoic acid consisting essentially of 4,4 bis(4- hydroxyaryl) pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1-5 carbon atoms.
- pentanoic acid consists essentially of 4,4 bis(4-hy-droxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of one carbon atom.
- composition of claim 1 wherein the pentanoic acid is 4,4 bis(4-hydroxyphenyl)pentanoicacid.
- composition of claim 3 wherein the natural resin acid is rosin.
- composition "of clai1nwhefe in the natuial resin acid. is abietic acid 7 Q V v A 6.
- composition of claim 3 ' wherein the polyhydric alcohol 'is ethylene glycol.
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Description
United States Patent .j
MIXED RESIN ACID ESTERS OF 4,4-BIS(4 HYDROXYARYL) PENTANOIC ACID Sylvan 0. Greenlee, Racine, Wis., assignor to S. C. Johnson & Son, Inc., Racine, Wis.
No Drawing. Application June 30,1955 Serial No. 519,279
9 Claims. Cl. 260-24) This invention relates to new compositions which are mixed esters ofpolyhydric alcohols, natural resin,acids,
reaction products having unusually good chemical resistance, hardness, gloss, etc.
These and other objects and advantages are attained by the present invention, various novel features of which will become more fully apparent from the following description, with particularreference to specific examples which are to be considered as illustrative only.
The compositions of this invention, being esters of polyhydric alcohols and mixtures of natural resin acids and hydroxyaryl-substituted aliphatic acids, are relatively high molecular weight resinous polyhydric phenols. The number of phenolic groups per molecule. are dependent on the number of alcoholic hydroxyl groups present in the polyhydric alcohol esterified, as well as on the amounts and proportions of natural resin acid and hydroxyaryl-substituted aliphatic acid used in the preparation of the esterified product.
The mixed esters of this invention combine within the same chemical molecule natural resin acid esters and a phenolic residue, the natural resin acid ester portion being similar to the natural resin acid portion presentin the so-called ester gums which are natural resin acid esters of polyhydric alcohols. This property renders the compositions of this invention particularly valuable in the manufacture of complex products such as coating and molding compositions, where the natural resin acid esters are desirable for the purpose of contributing hardness and gloss to the finished product. The phenolic residues present in the compositions and introduced by the hydroxyaryl-substituted aliphatic acids contribute reactive phenolic hydroxyl groups which for the most part do not enter into the esterification reaction used in the preparation of the mixed esters of this invention. These functional groups permit further reaction between the mixed esters of this invention and such materials as aldehydes, epoxides, and carboxylic acids to yield additional complex products. Reaction with aldehydes, either in' the presence or absence of other compounds capable of polymerization with aldehydes, gives compositions which are valuable constituents of protective coatings and molding resins. Similarly, the phenolic hydroxyl groups of the phenolic residues may be reacted with polyepoxide compositions to give highly polymerized products containing within the same molecule the natural resin acid esterresidues. Esterification of the phenolic hydroxyl groups of the phenolic residue with dibasic acids would also give polymerization in which the natural resin acid ester becomes an intimate part of the final polymer chemical composition. Such esterification reactions involving the phenolic hydroxyl groups would conveniently be carried out by heating with a mixture of the dibasic acid and acetic anhydride.
The hydroxyarylsubstituted aliphatic acids contemplated for use in preparing the desired resinous polyhydric phenols have two hydroxyphenyl groups attached to a single carbon atom. The preparation of these substituted acids may be most conveniently carried out by condensing a keto-acid with the desired phenol. Experience in the preparation of bisphenols and related compounds indicates that the carbonyl group of the ketoacid must be located next to a terminal carbon atom in order to obtain satisfactory yields. A terminal carbon atom as used herein refers to primary carbon atoms other than the carboxyl carbon atom of the keto-acid. Prior applications, Serial Nos. 464,607 and 489,300, filed October 25, 1954, and February 18, 1955, respectively, disclose a number of illustrative compounds suitable for use as the hydroxyaryl-substituted acid, and methods of preparing'the same. These materials, which are referred to for convenience as Diphenolic Acid, or DPA a trademark of S. C. Johnson & Son, Inc., comprise the condensation products of levulinic acid and phenol, substituted phenols or mixtures thereof. It is to be understood that the phenolic nuclei of the Diphenolic Acid may be substituted with any groups which will not interfere with the esterification reactions. For example, the nuclei may be alkylated as disclosed in Serial No. 489,300 or they may be halogenated. The Diphenolic Acid derived from 1 mol of levulinic acid and 2 mols of phenol is particularly advantageous in that it may be readily prepared to a high degree of purity, whereas the use of substituted phenols, such as the alkylated products, usually results in. mixed compositions which are less readily purified. On the other hand, there are cases Where the Diphenolic Acid derived from alkylated phenols are more desirable than those derived from the nonalkylated product on the basis that the alkyl groups tend to give better organic solvent solubility, flexibility, and better water resistance.
The natural resin acids which may be used with these hydroxyaryl-substituted acids in the co-esterification of the polyhydric alcohols are illustrated by the commercial grades of rosin and other natural-occurring acid resins, such as the kauri, copal, damar, and Congo gums. Typical commercial grades of rosin, for example, have acid values of, around 150-175. Acid values as used herein are defined as the number of milligrams of KOH required to neutralized the acid present in a one-gram sample. Typical damar gums have acid values ranging from 18 to 60. Kauri gums have acid values of from 60-80, while copal gums have acid values in the range of -130. The essential composition or" all these natural-occurring resin acids are cyclic terpenic type acids of which abietic acid is fairly typical.
The polyhydric alcohols may be the nonresinous type or the resinous type. These polyhydric alcohols, because of their polyfunctionality, will esterify with natural resin acids and hydroxyaryl-substituted acids to give a resinous phenolic product. Illustrative of the nonresinous type polyhydric alcohols are such materials as ethylene glycol, polyethylene glycols, propylene glycol, polypropylene glycols, 1,3-butane diol, 2,5-pentane diol, 1,6-hexane diol, neopentyl glycol, glycerol, erythritol, pentaerythritol, polypentaerythritols, sorbitol, mannitol, alpha methyl glucoside, polyallyl alcohols, diethanolamine, triethanolamine, and tetramethylol cyclohexanol The resinous p y y alcohols Which y be used Esterifieation of either the nonresinous or resinous in the preparation of the subject esters may be illustrated polyhydric l h l with Di henoli A id and natural y Such materials as the l'esinells Ieaetion Products of resin acids is conveniently carried out by direct heating st e v yp nyl) p py With ethylene ch10 at temperatures of from 190275 C. under conditions Tohydriil g y mofieehlofohydrin- The reaction 5 where the water produced during condensation is continuef the Same. dihydrie Phenol with epichlorohydfln or ously removed as it is formed. In the case where epl i' 'die'hlofohydfin gives resinous p y y a100- oxide groups of, for example, a resinous composition of H015 which Polymeric p y y alcohols and Which the Epon resin type produced by Shell Chemical Corpoin some cases. addition to the alcholic y y p ration are partially esterified only to the, extent of one 'eollt'ain ePOXide p epoxidereenwinihg P carboxyl group reacting with one epoxide group, lower nets are 'well illustrated by the commercially availa le temperatures may b d d no ater i formed since Epon resins marketed y Shell Chemical Corporation) the reaction of the carboxyl group with the epoxide The preparation of these resinous p y y alcohols are group is that of direct addition with the formation of an described in US. Patents 2,456,408, 2,503,726, 2,615,008, ester-linkage and a free hydroxyl group. Since the Di- '2,6'68,805, 2,668,807 an 2693,315- phenolic Acid and the polyhydric alcohols have boiling Other resinous p y y which y be points which are in all cases above 190 C., the Water ployed may be illustrated by those which are prepared b r d by rmitti itto olatilize during esby the'reaction of phenol-formaldehydecondensates with teriiication, Rgmoval f thelwam-vmayp also-be fadchlorohydrins. For example, analkylphenol m y b Contated by continuously bubblin gthrough the reaction mixdells'ed With formaldehyde, followed y treatment of 8m ture during esterification a stream of inert gas, such as alkaline solution of this intermediate methylol derivative carbon di id nitrogen, It is al o sometimes conven- With chlerohydrln, Such as glycerol'mollqehlorohydfini lent to. facilitate the water removal bycarrying out the to y d after condensation a Polymeric p y y aleoreaction in a vessel provided. with condenser attached 'hol. This resinous polyhydric alcohol may then be'used thereto through a water trap, adding a suflicient amount in esterification with the diphenolic acids to prepare the of a volatile, water-insoluble. solvent to give reflux at the subject resinous polyhydric phenols; esterification temperature, continually removing the wa- A yp formula for a p i n r n descri ter by azeotropic distillation and permitting the solvent may be illustrated by the following reaction between equal to return to the reaction mixture after having dropped the molar portions of ethylene glycol, abietic acid, and 4,4- water in the water trap. V bis(4-hydroxyphenyl)pentanoic acid. Abietic acid is the The order of addition of the various ingredients, Di- "chief acid ingredient of commercial rosin and is typical phenolic Acid, resin acids, and polyhydric alcohols, to of the terpenic type acids present in the natural resin each other may be varied. It is sometimes advantageous acids. to vary this order of addition to obtain optimum results H3O GOZH HOG onioniooin H 0 0 V on OH OH heat C +l 1 ll a A g on on,
CH3 0 on,
H: no onioniooionionioio on CHzOH H1O C I' ("JH on HiiG 0-0 a C s a From the above formula it will be obvious that use of with the particular combination of ingredients used. In more complex polyhydric alcohols, such as glycerol, the art of high temperature esterification, it is sometimes pentaerythritol, and the polypentaerythritols, would give advantageous to use certain esterification catalysts, and higher molecular weight products in which the ratio of these'may be used in the preparation of the compositions Diphenolic Acid to natural resin acid may be varied of this invention.
through wide ranges. It is understood that the composi- The following examples will serve to illustrate this intions obtained by co-esterification of polyhydric 'alcovention, however, 'it should be understood that the inhols with Diphenolic Acid and the natural resin acids vention. is not intended to be limited thereby; In'the give mixed products, including to some extent esterificaexamples, proportions expressed are parts by weight un tion of the phenolic hydroxyl groups of Diphenolic Acid less otherwise indicated. i
with the carboxyl groups of diphenolic acid itself as well Examples I to VI illustrate the preparation of some as esterification of the alcoholic 'hydroxyl groups by the polyhydric alcohol esters of inixturesof Diphenolic'Acid natural resin acids. For the most part, however, the more 7 and-natural resin acid esters. These reactions are in all reactive alcoholic hydroxyl groups of the polyhydric al cases carried out in vessels provided with a thermometer, 'cohols tend-to-esterify to a greater extent than the phenola mechanical agitator, and a condenser attached through ydroxyl groups. These compositions are valuable in a water trap. Inert gas was bubbled through the reacform'ulating useful products in the coat ngs, molding, tion mixtures throughout esterification so as to remove and adhesive field. l water formed in the esterification.
Example 11 A mixture of 143 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid, 165 parts of commercial rosin, and 34 parts of ethylene glycol was esterified to an acid value of 7 yielding a product having a softening point of 81 C.
Example III In a reaction vessel provided with a mechanical agitator was placed 452 parts of bis(4-hydroxyphenyl)isopropylidene dissolved in 1500 parts of water containing 82 parts of sodium hydroxide. The temperature of the continuously agitated solution was raised to 60 C. and 93 parts of epichlorohydrin was added slowly at 60-65 C. After addition of the epichlorohydrin was complete, the temperature was gradually raised to 95 C. and held at this temperature for a period of 1 hour. A solution of 82 parts of sodium hydroxide dissolved in 500 cc. of
water was added, lowering the temperature to 73 C. at which point 161 parts of ethylene chlorohydrin was added slowly over a period of 28 minutes. After all of the ethylene chlorohydrin had been added, the temperature was gradually raised to 95 C. and held for 1 hour. The unreacted caustic was neutralized by adding 100 parts of 37% aqueous HCl and the product was washed several times with hot water to remove the salt and excess HC]. The product was finally dried by heating with agitation giving 558 parts of a product having a softening point of 56 C.
To the 558 parts of this polymeric polyhydric alcohol was added 360 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid and 415 parts of a commercial grade of rosin having an acid value of 160, and the resulting mixture esterified to an acid value of 6.4. The product had a softening point of 102 C.
Example IV A mixture of 143 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid, 165 parts of commercial rosin, and 37 parts of pentaerythritol was esterified to an acid value of 7.5 to yield a product having a melting point of 126 C.
Example V Example VI A mixture of 174 parts of Epon 1004 and 101 parts of commercial rosin was esterified to an acid value of 19 at which point 86 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid was added and esterification continued until an acid value of 139 was reached, giving a product having a softening point of 131 C. I
The remaining examples illustrate the preparation of more complex products by the reaction of the mixed esters of this invention with formaldehyde, to produce a resinone composition useful in the manufacture of protective coatings; It will be understood, of course, that the phenolic hydroxyl groups of themixed esters may be reacted with other materialssuch as epoxides or other acids, to give various other reaction products. These products generally possess the hardness and ,gloss characteristic of natural resin esters and show other exceptional properties such as flexibility, chemical resistancaetc.
Example VII A mixture of parts of the resinous product of Example I, 21 parts of 38% aqueous formaldehyde, .063 part of oxalic acid and 17 parts of xylol was heated with continuous agitation for a period of 1 hour and 30 minutes at 95 C., after which the water layer was removed by decantation. The organic resin layer was heated with agitation to C. at a reduced pressure of around 30-40 mm. in order to remove the last traces of water.
A mixture of 10 parts of this formaldehyde reaction product and 10 parts of linseed oil was heated with agitation for 30 minutes at 240-280 C. at which point 10 parts of China-wood oil was added and agitation continued until the mixture had cooled to 228 C., and this temperature held for 15 minutes. This product was dissolved to 50% nonvolatile content in a solvent composed of equal weights of xylol and a high boiling naphtha (boiling range -225 C. and an aniline point of 60 C. to a viscosity of A-3 Gardner-Holdt bubble viscometer). This varnish was treated with 03% cobalt naphthenate drier and 3% lead naphthenate drier based on Example VIII Replacing the resinous product of Example I with the resinous product of Example II in the reaction with formaldehyde, and final cooking with the drying oils, as in Example VII, gave a product which formed flexible air-dried films which withstood boiling water for a period of 1 hour.
The mixed esters of this invention may be modified to some extent by incorporating with the esters other constituents. These constituents maybe inert constituents such as fillers, pigments, or certain plasticizers, or they may contain functional groups and enter into the esterification of the polyhydric alcohols with natural resin acids and hydroxyaryl-substituted acids so as to be chemically carried by the mixed esters of this invention.
It should be appreciated that while there are above disclosed only a limited number of embodiments of this invention, it is not intended to be restricted thereto, and that it is intended to cover all modifications of the invention which would be apparent to one skilled in the art and that come within the scope of the appended claims.
It is claimed and desired to secure by Letters Patent:
1. A new composition of matter comprising the mixed ester of a fusible polyhydric alcohol, a natural resin acid, and a pentanoic acid consisting essentially of 4,4 bis(4- hydroxyaryl) pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1-5 carbon atoms.
2. The composition of claim 1 where the pentanoic acid consists essentially of 4,4 bis(4-hy-droxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of one carbon atom.
3. The composition of claim 1 wherein the pentanoic acid is 4,4 bis(4-hydroxyphenyl)pentanoicacid.
4. The composition of claim 3 wherein the natural resin acid is rosin.
. 5. The composition "of clai1nwhefe in the natuial resin acid. is abietic acid 7 Q V v A 6. The composition-ofclaimj wherein the polyhydiiic alcohol is a polyglycidyl ther of a member of the group consisting of polyhydr ic phenols and polyhydric alcohols. 7. The composition of claim. 3- wherein-the polyhydric alcohol is.g1'yce '-ol.
8. The composition of claim 3 'wherein the polyhydric alcohol 'is ethylene glycol.
9-. The coinp'ositionbf -clgirn 3 wherein the polyhydric alcohol is pntaerythritbl; I
7 No references cited.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,907,738
October 6, I959 Sylvan 0. Greenlee It is hereby certified that err of the above numbered patent requiri or appears in the-printed specification Patent should ng correction and that the said Letters read as corrected below. Column 2, line 52, for "neutralized" read neutralize column 3, line 25, for "diphenolic acids" read Diphenolic Acid line 68, for "d' iphenolic acid" read Diphenolic Acid Signed and sealed thia 14th day of June 1960.
(SEAL) Attest: KARL "I1. AXLINE ROBERT C. WATSON \ttesting Officer Commissioner of Patents
Claims (1)
1. A NEW COMPOSITION OF MATTER COMPRISING THE MIXED ESTER OF A FUSIBLE POLYHYDRIC ALCOHOL, A NATURAL RESIN ACID, AND A PENTANOIC ACID CONSISTING ESSENTIALLY OF 4,4 BIS(4HYDROXYARYL) PENTANOIC ACID WHEREIN THE HYDROXYARYL RADICAL IS A HYDROXYPHENYL RAIDCAL AND IS FREE FROM SUBSTITUENTS OTHER THAN ALKYL GROUPS OF FROM 1-5 CARBON ATOMS.
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US519279A US2907738A (en) | 1955-06-30 | 1955-06-30 | Mixed resin acid esters of 4, 4-bis(4-hydroxyaryl) pentanoic acid |
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US519279A US2907738A (en) | 1955-06-30 | 1955-06-30 | Mixed resin acid esters of 4, 4-bis(4-hydroxyaryl) pentanoic acid |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3226179A (en) * | 1962-10-01 | 1965-12-28 | Huyck Corp | Papermaker's felt, woven fabrics and fibers of wool modified with an aldehyde - 4,4 - bis(4 - hydroxy phenyl) pentanoic acid reaction product and the production thereof |
US3433766A (en) * | 1955-04-20 | 1969-03-18 | Minnesota Mining & Mfg | Derivatives of bisphenolic substituted carboxylic acids |
US6562888B1 (en) | 1998-07-27 | 2003-05-13 | Arizona Chemical Company | Light-colored rosin esters and adhesive compositions |
-
1955
- 1955-06-30 US US519279A patent/US2907738A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
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None * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3433766A (en) * | 1955-04-20 | 1969-03-18 | Minnesota Mining & Mfg | Derivatives of bisphenolic substituted carboxylic acids |
US3226179A (en) * | 1962-10-01 | 1965-12-28 | Huyck Corp | Papermaker's felt, woven fabrics and fibers of wool modified with an aldehyde - 4,4 - bis(4 - hydroxy phenyl) pentanoic acid reaction product and the production thereof |
US6562888B1 (en) | 1998-07-27 | 2003-05-13 | Arizona Chemical Company | Light-colored rosin esters and adhesive compositions |
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